Complex metal compounds of monoazo triazine dyestuffs



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United States Patent COMPLEX METAL COMPOUNDS or MONOAZO V t TRIAZINEDYESTUFFS Oesterlein, Basel, Switzerland, assignor Ciba This inventionprovides new complex metal compounds of monoazo-dyestufis' of theformula in which R'OH represents the radical of a hydroxynaph- *thalenesulfonic acid which is bound to the azo linkage in a position vicinal tothe hydroxyl group and contains a 'nitro group, and A represents theradical of an aminocompound which contains a group imparting solubilityin Water and is bound'to the azo linkage in a position vicinal to ahydroxyl group and of which the amino group iS'bOuHd to a halogenated1:3:5-triazine radical. The invention advantageously provides copper ornickel com pounds of the above kind, and especially 1:2-complex chromium,oricobalt compounds thereof, and especially such complex metalcompounds of monoazo-dyestuifs of the formula I I in' which rt is awhole number not greater than 4, ,1; represents a naphthalene radicalbound to the azo linkage a position vicinal to a hydroxyl group, and Xrepresents a chlorine atom or advantageously an amino group twhichmay besubstituted. 7 a

:The new metalliferous monoazo-dyestuffs can be ob,-

tained by metallizing the corresponding metal-free dyestufl s orespecially advantageously by reacting -ofthe formula 'i (a); f N

which R1 represents a free amino groupjor,

radical or a halogen ato'mQon'the one hand,

complex heavy metal compound of a monoa'zo-dyestulf of the formula a iN-Aj,

in which R-OH represents the radical ofa hydroxynaph tion vicinal to thehydroxyl group and containinganitro group, and A represents the radicalof an amino-com.- pound which contains a sulfonic acid group and isbound ,tothe azo linkage ina position vicinal to a hydroxyl group, andof which the amino group is atmost secondary,

and, when a trihalogen triazine is used as saningma:

terial, desired, reacting the product, on the other hand, 7 d a with amercapto compound, a hydroxyl compound, an

m'onia or an at most secondaryv monamine.

When a. dihalogen triazine of the Formula 3 isliusedj;

5 it "advantageously contains 7 as the substituent Rfthe radical of;angarnine or a free amino group. @These selves known from a cyanurichalide suchas cyanuric bromide? or cyanuric chloride, by reacting onemol of d 10 cyanuricj halide; with one mol of ammonia or ofare activeorganic hydroxyl compound, for example, a phenol oranalcohol, or withone mol of an at most secondary monamine. 1 Assuch amines there may beused, for example, methylarnine, ethylamine, isopropylamine,methoxyethylamine, methoxypropylamine, cyclohexylamine,

dimethylamine, diethylamine or N-methylphenylamine, chlorethylamine,ethanolamines," 'aminocarbonic acid esters, aminoacetic acid ethylester, aniline, aminoethane sulfonic acid, N-methylaminoethane sulfonicacid, aminosalicylic acid, ortho-, metaorpara-aminobenzoic acid, 7

aminoberizoic acid sulfonic acids, ortho-, metaor paraaminob'enzenesulfonic acid or I-aminobenzene-Zti-disulfonic acid," and alsoaminonaphthalene mono dior tri-sulfonic acids. Q 1 26 The metalliferousdyestuffs to be condensed with'the cyanurichalide or a primary cyanurichalide condensation product of the Formula 3 can be made by methods inthemselves known,'for example, by metalli'zing monoazodyeStutfs of theformula i a f 5) p i V N 'x." -in which; OH represents the radical ofa-hydroxynaph- -thalene 'sultonicacid which isboun'd to theazoilinkagein -a positionvicinal'to the h'ydroxylgroup and contains a nitro group,and A representszthe radicallof' an aminocompound which contains asulfonicacid' group and bound to "the azo linkage in a position vicinalto a hydroxyl group and' of which the amino group is capable '"ofbeing-acylated. For making metallizable'monoaaodyestuils of the Formula5 a diazotized' nitro-aminonaphthol sulfonic 'acid, especiallydiazotized' 6-nitro- 1' arnino-2-hydroxynaphthalene-4-sulfonic acid,may-be coupled in an alkaline medium-for example, a medium 5 containingsodium hydroxide, calcium hydroxideQr'nagnesium hydroxide or potassiumhydroxide, with acoupling component which is capable of coupling in aposition vicina'l toa hydroxylgroup or enoli'zable keto group, andcontains an acylatable' amino group 'or'a substit'uent, 'for example; anacylamino group convertible into an 'acyla'table amino group "afterproduction of the -dyest'utfh As isuch coupling components there may bementioned, for example, 1 acetoacetylamino-B amincbenzenei-sulfonicacid, 1-t(3'- or 4'- aminophenyl) 5 pyrazolone-3ecarboxylic acid;"2-amino 5 hydroxynaphthalenefl-sulfonic acidff r Iamino-i-hydroxynaphthalene-7 Ldisulfoni'c acid, 2- (3f;f6r 4fa'rhinobenzbylamino) hydroxynaphthaleneJ sul .acid,j2(4Gacetylaminophenylamino) -5-hydroxyna lene-t7 -sulfonic acid,2-(4'-aminophenylamino)'-5-hydr I naphthalene-327 disulfonic acid, 2(3'-,-au1inophe y 1-" I thalene sulfonic acid bound to the azo linkagein a po'si- 1 i x amino.) 5-hydroxynaphthalene-4?z7 disulfonic facid ramino-8 liydroxynaphthalene-3:6- or. 4:6{disulfom'c c The-conversion ofthe dyestuffs obtainedf rom components into the complex heavyrnetalcompo 7 usedvas starting materials in the proc'ess tof this invencan' be carried out while the dyestuffs arjelpre coupling mixture in 'whicli mey'we'ie formed;

" A 94 ,085; I V Patented Ju 'dihalogen triazines can be prepared bymethods in theu'racid, and especially aminonaphthol sulf onicacids'such.

tonic.

a As agents i lding metal there may be mentioned, m

cobalt, chromium, copper or pounds which contain one atom of metal incomplex I As agents yielding metal there maybe used, for 'example, saltswhich contain the said metals as the cation,

forcxample, chromium sulfates, cobalt acetate, cobalt sulfate, coppersulfate or copper acetate. In some cases 'it is of advantage to usecomplex metal compounds, for

example, in the form of metal-ammine complexes; such ascopper tetramminesulfate obtained from copper sulfate and ammonia, pyridine ormonoethanolamine, or in the form of compoundswhich contain one of theaforesaid metals bound in complex union in the anion, for example,complex chromium compounds of organic hy .droxy-carboxylic acids such assalicylic acid, or complex cobalt or copper compounds of alkali salts ofaliphatic 'amino-carboxylic acids or hydroxy-carboxylic acids, such "asglycine, lactic acid or above all tartaric acid, such as sodium coppertartrate.

'The treatment with the agents fyielding metal may be carried out by amethod in itself known, for example, at room 'temperature andadvantageously by heating at a temperature within the range of 50- C. to120 C. under atmospheric pressure, for example, under reflux 'or; ifdesired, under superatmospheric pressure, the pH-value depending on thenature of the metallization process used. For example, an acid mediuminthe case of copper sul- -fate and-an alkalinemediuniin the case ofcopper'tetramrmineI-sulfate. .If'desired, the metallization may 'be car-'"riedout in the presence of a: solvent, for example alco- -hol,dimethyl fotmamide .etc.

The starting? materials containing hea metal can also be prepared by themetallization and simultaneous or subsequent hydrolysis of.orthozorthd-dihydroxy- .monoazo-dyestufis of the kind definedabovewhich contain :acylamino groups.

The condensation of the complex metal compounds of imonoazo-dyestufis ofthe Formula 4 or 5 with the halogentriazines of the Formula 3 isadvantageously carried out .in the presence of an agent capable ofbinding acid, such .as sodium acetate, or sodium hydroxide or carbonate,and under conditions such that at least one exchangeable halogen atomremains in the final product, thatis to say, for example, in thepresence of an organic solvent or at a relatively low temperature in anaqueous medium.

The dyestufis of this invention are new and are useful for dyeing a verywide variety of fibrous materials, .such as cellulose, regeneratedcellulose or viscose, linen and especially cotton. They are suitablefor-dyeing by the so-called direct dyeing method from a long'liquor inan aqueous alkaline bath, which may contain a high concentration of asalt, and especially by the printing method or pad dyeing method, inwhich the dyestuff is applied to .the material to be dyed andsubsequently fixed thereon by means of an acid-binding agent and, ifdesired, by the .action of heat.

The dyeings produced with the dyestuffs'of this invention on cellulosicfibers are generally distinguished by their good fastness to light andabove all their excellent fastness to washing. The resistance of thedyeings on cotton to anti-creasing dressings is remarkable. .Thedyestufisare. also suitable for .dyeing nitrogenous textile .ma-'terials, such as silk, superpolyamide fibers, wool or the like, fromweakly acid to neutral baths, if desired, in the presence of the usualdyeing assistants.

.The following examples illustrate the invention, the "parts andpercentages being by weight:

A w r,

4 Example 1 29.5 parts of the diazo-compound of nitrated l-amino-2-hydroxynaphthalene-4-sulfonic acid are added as the sodium salt to23.9 parts of 2 -amino-5-hydroxynaphthalene-7-sulfonic acid in partsbyvolume of a 2 N-solution of sodium hydroxide, :and coupling is carriedout at 15-20 C. When the coupling is finished the dyestuff isprecipitatedby the addition of sodium chloride, then filtered ofi,and'purified by washing with sodium chloride solution of 5% strength. 7

53.4. parts of the (lYtiSl'UlfSOQOblfllIlCd aredissolved in 1500 partsof water and 50 parts of sodium acetate are added. After "the additionof 25 parts of copper sulfate (crystalline) the whole is heated for onehour at 60-80 C. The'copper complex is salted out and filtered off, Thepaste so obtained is dissolved in 2000' parts of water and the solutionis rendered Weakly alkaline. At 5-l0 C. there are added 185 parts ofcyanuric chloride dissolved in 100 parts of acetone, and the reactionmixture is neutralized by the addition of a dilute solution of sodiumcarbonate. When the condensation is finished, the dichlorotn'azinedyestuff is precipitated by the addition of sodium chloride, filteredoff, mixed with 5 parts of monosodium phosphate and 5 parts of disodiumphosphate, and the mixture is dried in vacuo at 40 C. The dyestutf soobtained dyes cotton from alkaline baths containing a salt, violet tintswhich are fast to washing.

By .adding to the resulting solution of the dichlorotriazine compound aneutral solution of 17.3 parts of l- ;aminobenzene-3-sulfonic acid, andmaintaining the reaction mixture weakly alkaline for 3 hoursat 30-40?0., there is obtained a monochlorotriazine dyestufl which dyes cottonviolet tints that are fast to washing andlight.

-Example 2 29.5 parts of'the nitrated diam-compound of l-amino-2-hydroxynaphthalenea l-sulfonicacid are added as the sodium salt to23.9 parts of Z-arnino-S-hydroxynaphthalene-7-sulfonic acid in 100 partsby volume of 2 N-solution of sodium hydroxide, and coupling is carriedout at 15-20 C. When the coupling is finished the dyestuff isprecipitated by the addition of sodium chloride, then filtered off andpurified by washing with sodium chloride of 5% strength. 53.4 parts ofthe resulting dyestufi are d1ssolved 1n 300 parts of water at 80 C. andparts of a'solution of sodium chromosalicylate having a chromium contentof 2.6% are added. After boiling the mixture for 4 hours under refluxthe chroming is complete.

In order to prepare the dichloro-triazine derivative, the resultingsolution of the 1:2-chromium compound is adjusted to a pH value of 7with dilute hydrochloric acid. 18.5 parts of cyanuric chloride,dissolved in a small amount of acetone, are added at 0-5" C. whilestirrmg well, and the pH value is maintained at 7 by the dropwiseaddition of 50 parts of a 2 N-solution of sodium hydroxide. After theaddition of 5 parts of monosodium phosphate and 5 parts of disodiumphosphate the solution is evaporated to dryness in vacuo at 30-40 C.

The new dyestutf so obtained is a. grey-black powder, and dyes cellulosefibers by the process described in Example 8 greenish grey tints of goodfastness to washingand'light. 3 Example 3 In order to prepare themonochlorotriazine derivative of the dyestutf obtained as described inExample 2, the solution of the 2:1-chromium compound obtained asdescribed in the first two paragraphs of Example 2 {is adjusted to apH-value of 7 with dilute hydrochloric acid. 18. 5 parts of cyanuricchloride dissolved in a small amount of acetone are added at 0-5 C.while stirring well, and the pH value ismaintained at 7 by the drop-Wise addition of 0 Pa ts of a 2 .N-solution of sodium hydroxide. l

,are added. After stirriug'the whole" endl for 3 hours at -40 C.Bygevaporating the mixture to dryness in vacuo at -50" C., thenewdyestufl is obtained as a grey-black powder which-,dyescellulosefibers by the method described in Example 8 greenish grey tints of goodfastness to washing and light.

Example 4 53.4 parts of the dyestufi obtained as described in the 5.

first paragraph of Example 2 are dissolved at C. in 300 parts of ,waterwith the addition of parts of a '2 N-solutiouoffsodium hydroxide, and100 parts ofa cobalt sulfate solution having a cobalt content of 3.25%for V2 hour at 7080*C. metallization is Complete.

The corresponding dichlorotriazine compound can be obtained bythe methoddescribed, in the third paragraph of Example 2.

In order to the solution of the dichloro-triazine compound is mixed withparts by volume of a 2 N-solution of'arnmonia, and the whole is heatedfor 2 hours at 4Qf C., The dyestufi is isolated by evaporating thesolution in'vacuo. The

dyestufi dyescellulose fibers by the method described in 3 25 Example 8grey-brown tints'of good fastness to washing Example 5 Thedichlorotriazine compound preparedin known manner from 17.3 parts ofl-aminobenzene-B-sulfonic acid and 18.5'parts of cyanuric chloride areadded to the the solution obtained is evaporated to dryness in vacuo.

The dyestuifdyes cotton green-grey tints.

Further dyestuffs can beobtained in the manner described in Examples 1 5by converting the monoazodyestuffs, obtained from the nitrateddiazo-compound of 1-amino-2-hydroxy-naphthalene-4-sulfonic acid and thecoupling components given in column I of the following table, into.their complex metal compounds, the metals being given in column H,condensing the latter compounds with cyanuric. chloride, and reactingthe dichlorotriazine derivatives so'formed with'theamines given incolumn 111. The'condensation may be carried out in the reverse orderprepare the amino-chlorotria'zine compound I"\ J r V Coupling ComponentsMetal Amines Tints 5 2-Methylamino-5-hydroxy- Or Ammonia -gr eenish d vnaipihthalene i sultonic grey. ac

Do.. Or l-Aminobenzene-Zi- Do.

sulfonic acid. Do Ammonia;. brown- 1 r--- .isjhlt v o e 7.

2-Methylamino I5-hydroxy- Cu l-Aminobenzene-t violet. naircalht halenesulfonic g sulfouic acid. ac I Ni do I Do.

dro Or Ammonia greenish mm ew -hydroxynaph- (in Le of. success1on.. The,tints produced on cotton with these dyestuffs are glven 1n -I H 'i'I1.11 v 'III'Z IV. ".65

Coupling Components Metal Amines Tints 2-Am1no-6-hydroxynaph- -01Z-Aminoethanol greenish thaleue-7- sulionic acid. grey. -'CrDiethanolamine. Do.

-' Methylaminen Do.

Ethylamine. Do. ,Morpholiue. Do. "3-M et hoxypropyla-' 7 Do.

m ne. Isopropanolaminen"; Do. 1-Amiuob'enzene-2- Do.

sulfonie' acid. 2-Amlnoethanol gr Morpholine.-.

1-Aminobenzene-2- carboxylic acid. 2-Amiuonaphthalene- 4:8-disulitonicacid. Z-Aminonaphthalene- 6-sulfonic acid. Aniline D Ammnnial-Aminobenzenez- D sulfonic acid. 1-Aminobenzene-2.5- D0.

di-sulfonicaeid.-

' I f A solutionof 18*parts o'f2-methoxy-4:fi dichloro-l v th1:2;c0mplex chromium compound of 1 :13:. -V i 91:7 rand thewhole is.heated to 40? There are then added 10 parts of sodium bicarbonate andthe whole isheat'ed 6 disultonic 2 (4' Aminophenyl) 5 greenishhydroxynaphthaleneblue. 7:3' disulfonic acid.

z-Amino-a-hydroxynaph- .Cr. greenish -v mino-G-hydroxynaph- .Or 3Aminoethane-sul- Do. fonicacid.- Amino acetic acid.--" Do;4-Amlno-1-hydroxy- Do. .beuzene-Z-carbox: a:

ylic acid; Amino 4 -methyl 7 Do;

; -Example 6 triazine in acetone is r un into a neutral solutionfibtamed'a's"de'scribed in'th'e first'two paragraphs of Example), of

for 4 hours at 40 C. By Working up in the usual manner, there isobtained a. dyestufi tints. r q u v A dyestufi having" similarproperties is obtained by using, instead of Z-methoxy- }:6dichlorotriazine,thecor- V I responding quantityof,-""2.=.plienoxy-4:6-dichloro-1:3:S-

triazine or the corresponding quantity of 2-phenoxy-4z6adibromo-1:3:5-triazine or the corresponding quantity of Thecorresponding cobalt derivative dyes cotton violet- I grey tints. v I

romium which dyes cotton green-grey compo undo the:

brown-black tints.

in complex union per molecular proportion of dyestufi;

and 0.1 mol of the metal-free ,dyestuif of the formula k N no, r zoorrare dissolved in 2000 "parts of water. The whole is heated for one hourat 80-90" C. and the reactionmixture is maintained weakly alkaline bythe addition.of.sodium carbonate. A solution of the 1': Z chromium'mixed complex compound is formed, and the solution is cooled, 1

neutralized, and the complex compound is' condensed at 5 C. with 38parts of cyanuric chloride. The resulting solution isthen mixed with 240partsofaZN-solutibn of arnmoniaand heated for .2 hours :at C..Theaminochlorotriazine dyestuif so formed is'. obtained in" solid formby evaporating the solution in vacuo. -It dyes cotton Example 8 I 2parts of thedyestuff obtainedas dcscribed in the first two paragraphs ofExample 1 are dissolved in .100 parts of water. A fabric of regeneratedcellulosestabledibers is impregnated with the solution sopbtained n suchmanner that it takes up of its weight of the solution, and theimpregnated fabric is then dried. V

The fabric is then impregnated with a solution, at 20 C., containingper. liter, 10 gramsoflsod iurn hydroxide and 300 grams of sodiumchloride, the fahric is squeezed to a weight increase of 75%, the dyeingis steamed for 60 minutes at -10l C.',-rinsed, soaped for /1 hour,in'aiboiling solution of 0.3% strengthof a non-ionic detergent,rinsedand dried.

There is obtained a violet dyeing which is fast tiowash- 'ing and light.

By using 2 parts. of the dyestufi-obtained asdescribed in the firstthree paragraphs of Example 1, there is likewise obtained a violetdyeing which is fast to light and washing.

What is claimed is:

l. A complex heavy metal compound selected from the group consisting ofchromium and cobalt complexes, one

l N=N x A II, N

nois Hols N-c darn j on, N 7 our 5' I I p .v I j NO: r

atom of the metal of which is bound in complex union with two moleculesof monoazo-dyestufi, and nickel and copper complexes, one atom of themetal of which is bound in complex union with one molecule of monoazodyestuif, the said monoazo dyestuff corresponding to the formula I "HOarepresents I HOzS Hots -wlierein Y represents a member selected fromtheigroup consisting of a hydrogen atom and a sulfonicacid group, nrepresents a whole positive 'number up to 4, and X represents a2-arnino-4-chloro-l :3z5-triazine radical bound to thenitrogen-atombyits-6-position. v p

3. The complex copper compound which contains one atom of copper boundin complex union with one molecule of the monoazodyestufi of theformula.

4. A complex chromium compound which contains-one atom ofchromium'bound-in complex union with substantially two molecules-of-amonoa'zodyestufi of the formula wherein represents a member selectediromthe group Tconsisting of a hydrogen atom andasulfonic acid group,

n represents a whole positive number -up to 4, and.;X a2-amino-4-c'hloro lz3:S-triazine radical bound to the nitrogen atom byits 6-position.

5. A complex cobalt compound which contains-one atom of cobalt bound incomplex union with substantially two molecules of a monoazo dyestutf ofthe formula v 5p H01, 'n-I MH' wherein Y represents-a member selectedfrom the group consisting of a hydrogen atom aud a sulfonicacid group, nrepresents a whole positive number up to 4, and X represents a2-amino-4-chloro 1:'3;'S-triazine j radical bound to the nitrogen-atomby its 6-position.-

, 6. A complex chromium compound which contains one atom of chromiumbound in complex union with substantially two molecules of a monoazodyestufi of the formula wherein n represents a whole positive number upto 4 and X represents the 2:4-dichloro-1z3z5-triazine substituent. 7. Acomplex cobalt compound which contains one atom of cobalt bound incomplex union with substantially two molecules of a monoazo dyestuif ofthe formula OH OH H 035 HOxS NX n-iHiri wherein n represents a wholepositive number up to 4 and X represents the 2:4-dichloro-1:3:5-triazineradical.

8. A complex chromium compound which contains one atom of chromium boundin complex union with substantially two molecules of a monoazo dyestufiof the formula OH OH H O as H 018 V N-X xa-lHln-l wherein n represents awhole positive number up to 4 and X represents a2-amino-4-chloro-1z3z5-triazine radical bound to the nitrogen atom byits G-position. V

9. A complex cobalt compound which contains one atom of cobalt bound incomplex union with substantially two molecules of a monoazo dyestufi ofthe formula on no Hols Ho's lg-x v wherein n represents a whole positivenumber up to 4 and X represents a 2-amino-4-chloro-1:3 :S-triazineradical bound to the nitrogen atom by its 6-position.

10. The complex chromium compound which contains one atom of chromiumbound in complex union with substantially twomolecules of the monoazodyestufi of the formula OH HO E] H015 H018 C I-NH:

11. The complex cobalt compound which contains one atom of cobalt boundin complex union with substantially two molecules of the monoazodyestuif of the formula OH HOaSf 12. The complex chromium compound whichcontains one atom of chromium bound in complex union with substantiallytwo molecules of the monoazo dyestufi of the formula References Cited inthe file of this patent UNITED STATES PATENTS 2,270,478 7 2,273,115Kra'cker et a1. Feb. 17, 1942 Schmid Ian. 20, 1942'

1. A COMPLEX HEAVY METAL COMPOUND SELECTED FROM THE GROUP CONSISTING OFCHROMIUM AND COBALT COMPLEXES, ONE ATOM OF THE METAL OF WHICH IS BOUNDIN COMPLEX UNION WITH TWO MOLECULES OF MONOAZO-DYESTUFF, AND NICKEL ANDCOPPER COMPLEXES, ONE ATOM OF THE METAL OF WHICH IS BOUND IN COMPLEXUNION WITH ONE MOLECULE OF MONOAZO DYESTUFF, THE SAID MONOAZO DYESTUFFCORRESPONDING TO THE FORMULA